Nu-substituted oxyacetamide compounds and insect control compositions



atented Oct. 11, 1949 UNITED STATES TENT OFFICE N-SUBSTITUTEDOXYACETAMIDE COM- POUNDS AND INSECT CONTROL COM- POSITIONS Lowell B.Kilgore, Washington, D. 0., assignor, by mesne assignments, to Lowell B.Kilgore and Helen Ford Kilgore, both of Washington, D. C.

No Drawing. Application April 27, 1945, Serial No. 590,721

(Cl. l6730) 13 Claims.

wherein R. is aralkyl, and R is a hydrocarbon radical. A further objectof this invention is to provide processes for the preparation of thesenew compounds. Still a further object of this invention is thepreparation of new and useful chemicals which possess insect combatingproperties to a high degree. Other objects and advantages of theinvention will hereinafter appear.

These objects may be accomplished by reacting an a-etherified aceticacid with a primary amine so as to eliminate a molecule of water asfollows:

The same objects may also be accomplished by reacting an amide-formingderivative of an aetherified acetic acid, such as the acyl halide, acidanhydride, or the ester of a volatile alcohol with a primary amine.These methods of preparing my new N-substituted a-etherified acetamidesare characterized by the following equawherein Y is the hydrocarbonresidue of a volatile alcohol and X is halogen.

Still another means which I have discovered of attaining the objects ofthis invention comprises reacting the proper N-substitutedm-haloacetamide with the alkali oxide of the requisite alcohol as shownby the following equation:

wherein Me represents an alkali metal and X is halogen. In the foregoingEquations 1, 2, 3 and 4, R and R represent either the same or differentorganic radicals.

The various means of obtaining the objects of this invention will bemore readily understood by the following showing of detailed exampleswhich, however, do not limit the scope of the invention in any way.

EXAMPLE 1 Preparation of N-isobatyl phenethoxyacetamide 5.3 grams ofthionyl chloride was added to a solution of 8 grams of phenethoxyaceticacid dissolved in cc. of benzene. After refluxing for 2 hours, theexcess thionyl chloride together with 25 cc. of benzene was distilledoff. 3.2 grams of isobutyl amine were added to the phenethoxyacetylchloride and the mixture refluxed for '7 hours. It was washed withdilute HCl and water and then distilled under reduced pressure. 8 gramsof product boiling at -148 C./1 mm. were obtained.

EXAMPLE 2 Preparation of N-beneyl benzoxyacetamide 18 grams of methylbenzoxyacetate were refluxed with an excess of benzyl amine. During thisrefluxing the methanol of reaction was slowly distilled off. Thereaction mixture was diluted with benzene, washed with dilute H01, andthen water, and fractionated under reduced pressure. 12 grams ofN-benzyl benzoxyacetamide boiling at IOU-103 C./1 mm. were obtained.

EXAMPLE 3 Preparation of N-dodecyl benzoxyacetamide 20 grams of methylbenzoxyacetate were refluxed with 18 grams of dodecyl amine. During thisrefluxing the methanol of reaction was slowly distilled off. Thereaction mixture was diluted with benzene and fractionated under reducedpressure. 8 grams of N-dodecyl benzoxyacetamide boiling at 210-15/2 mm.were obtained.

Other members of the new series of N-substituted a-etherified acetamideswhich I have prepared by the methods set out in detail in theaforedescribed examples are:

N-amyl benzoxyacetamide N-allyl benzoxyacetamide N-cyclohexylbenzoxyacetamide N-phenyl phenethoxyacetamide I have discovered that thenew N-substituted a-etherified acetamides of my invention, as a class,possess valuable insect toxicant and fugient properties. Furthermore thephysical properties of these compounds; such as odor and color aresuchas to make them unobjectionable for human use.

Table I demonstrates the eificacy of representative members of this newseries of organic compounds against the common house fly, Muscadomestica. The test procedure used was the Sandwich bait methodsubstantially as described in Soap, June 1939, p. 103 n. A coating ofmolasses was applied to one side of a strip of blotting paper and driedto a hard glossy surface. The molasses was then covered with a strip ofa special thin, porous paper which had previously been immersed'in apercent solution in alcohol of the compound to be tested and then drieduntil the alcohol had evaporated. The concentration of the testsolutions was reduced to 5 percent because the repellency of certainmembers of the series was so prolonged that the flies were in danger ofdying before completion of the test. For purposes of comparison onestrip was treated only with solvent and dried. The strips prepared inthis fashion Were mounted on a board and introduced into a large cagecontaining more than 2000 hungry house flies. By making observations atfrequent intervals the duration of repellency, that is the length oftime which elapsed before the flies began to feed on the molassesthrough the treated tissue was determined.

Table I Duration of Compound Repellency N -Amyl benzoxyacetamide 2 hr.15min. N Dodecyl benzoxyacetamide 5 hr. 40 mm N-Isobutylphenethoxyacetamide 4 hr. 30 mm N -Phenyl phenethoxyacetamide Not onlydo the compounds of my invention possess especially marked repellency tohouse flies, but they are also very effective against other annoyingpests such as the blackfly, mosquito, flea, red bug, gnat, and moth.

EXAMPLE 4 When applied to the forearm of an individual exposed to hungryAedes aegypti mosquitoes, N-isobutyl phenethoxyacetamide repelled theinsects for an average of 221 minutes.

EXAMPLE 5 Cloth impregnated with a solution comprising 1 gram ofN-dodecyl benzoxyacetamide dissolved in cc. of chloroform repelledhungry Aedes aegypti mosquitoes for 11 days.

Moreover I have discovered that these new N-substituted oc-EthEIlfiGdacetamides possess contact insecticidal properties. This wasdemonstrated by means of the Feet-Grady bio-assay technique using houseflies.

EXAlVl'PLE 6 solid carriers. They are especially useful as the activeingredients of insect-repellent lotions, creams, ointments and the like.They may be dissolved in liquid diluents such as alcohol, aqueousalcohol, isopropanol, dimethyl phthalate and hydrocarbon oils such askerosene or emulsified in Water, if necessary with the aid of a suitabledispersing agent. If desired they may be admixed with finely dividedcarriers such as diatomaceous earth, talc, pyrophylite, bentonite, etc.

Furthermore the new compounds of my invention may be combined withinsecticidal materials such as pyrethrum, rotenone, derris, cube, DDTand the like. Such a combination is particularly effective where theparalytic and lethal action of the insecticide is slow.

Although this invention has been described with referenceto illustrativeembodiments thereof it will be apparent to those skilled in the art thatthe principles of this invention may be embodied in other forms butwithin the scope of the appended claims.

What I claim is:

l. The N-substituted a-etherified acetamides having the general formula:

wherein R is aralykyl and R is an aliphatic hydrocarbon radical.

2. N -dodecyl benzoxyacetamide.

3. N -isobutyl phenethoxyacetamide.

4. N -amyl benzoxyacetamide.

5. An insect combative composition of matter comprising as essentialactive ingredient N- dodecyl benzoxyacetamide and a carrier therefor.

6. An insect combative composition of matter comprising as essentialactive ingredient N-isobutyl phenethoxyacetamide and a carrier therefor.

'7. An insect combative composition of matter comprising as essentialactive ingredient N-amyl benzoxyacetamide and a carrier therefor.

8. An'insect combative composition of matter comprising as essentialactive ingredient an N- substituted a-etherified acetamide having thegeneral formula:

wherein R is aralkyl and R is an aliphatic hydrocarbon radical,dissolved in an aliphatic alcohol.

9. An insect combative composition of matter comprising'as essentialactive ingredient an N- substituted u-GthBIifiGd acetamide having thegeneral formula:

wherein R is aralkyl and R is an aliphatic hydrocarbon radical,dissolved in a kerosene type hydrocarbon. I.

10. An insect combative composition of matter comprising as essentialactive ingredient an N- substituted a-etherifi'ed acetamide having thegeneralformula:

wherein I3. is aralkyl and R is an aliphatic hydrocarbon radical,dissolved in aqueous alcohol. 11. An insect combative composition ofmatter comprising an N-substituted alpha-etherified acetamide: havingthe general formula:

' 'Rj-o-oH2oo NHR' wherein R is aralkyl and R is an aliphatic hydrocarbon radical and a carrier therefor. Y

5 6 12. The N-substituted a-etherified, acetamides Number Name I Datehaving the general formula: 563,009 Bischler June 30, 1896 1,094,296Bergell Apr. 21, 1914 IPO CH2CONHR 2,120,512 Rosenhauer June 14, 1938wherein R is aralkyl and R is alkyl. 5 2,166,119 Bousquet July 18, 193913. An insect combative composition of matter comprising anN-substituted alpha-etherified FOREIGN PATENTS acetamide having thegeneral formula: Number u ry Date 501,004 Great Britain Feb. 10, 1939ROCH2CO-NHR 1 585,740 Germany Oct. '7, 1933 wherein R is aralkyl and Ris alkyl, and a car- OTHER REFERENCES rier therefor. :7

LOWELL KILGORE sldgwick, Orgamc Chemistry o f N1trogen (1937), pages136-140. (Copy 111 Division 6) REFERENCES CITED 15 Jour. Econ. Ent.,August 1940, pages 609-672,

h C D The following references are of record in the 5 2 52 z gg i z fi gi f Frankland file of this patent: et aL UNITED STATES PATENTS C. A.,V01. 23, page 134 0934), by Fischer 6t 31.

20 (Comes in Patent Ofilce Llbrary.) Number Name Date Jour. of Prak.Chem. (2) 65 (1902), pages 479 543,214 j t July 1895 and 480.(Copyin260-559,)

